Functional oxydisilethylene monomers



United States Patent 3,427,338 FUNCTIONAL OXYDISILETHYLENE MONOMERSCecil L. Frye, Midland, Miel1., assignor to Dow Corning Corporation,Midland Mich., a corporation of Michigan No Drawing. Filed Dec. 8, 1965,Ser. No. 512,529 U.S. Cl. 260448.2 12 Claims Int. Cl. C07d 103/02; C08g31/00, 51/74 ABSTRACT OF THE DISCLOSURE Cyclic silethylenesiloxanes inwhich alkoxy and functional halogens are present on the silicon atom.They are useful as additives to obtain copolymers which can bevulcanized at room temperature and for increasing desirable crosslinkingcharacteristics. Illustrative of a cyclic silethylenesiloxane is one ofthe formula CHaCHzCHaCHzO OCHzCHzOHzCHa The present invention relates tonovel cyclic silethylenesiloxanes and certain polymers thereof.

Cyclic organosiloxanes of the general formula wherein R is defined as amonovalent hydrocarbon radical, are well known as disclosed in U.S.Patent 3,041,363, June 26, 1962. In the prior art, R is restrictedsolely to hydrocarbon radicals and fails to include alkoxy and otherhydrolyzable or functional substituents.

It is an object of the present invention to introduce cyclicorganosiloxanes in which alkoxy and functional halogens are present onthe silicon atom. These novel cyclic organosiloxanes are useful in roomtemperature vulcanizing systems. For example, the functional monornersof this invention could be used as additives to obtain copolymers whichcan be vulcanized at room temperature. Relatively minor quantities canbe used wherein the resulting copolymer is rendered functional andexhibits the attendant advantages obtainable therefrom.

The novel monomers of this invention would be desirable as additives forcross-linking purposes. They are unique in that they have two types offunctional groups: (1) The hydrolyzable alkoxy or halogen substituentsand, (2) the strained SiOSi bond of the ring. These two types offunctional groups can be utilized independently by known methods andthus the compounds can be used to progressively cross-link siliconepolymers.

These and other related objects will be apparent from the followingdetailed description of the invention.

The novel compounds of this invention are of a formula selected from thegroup consisting of and Patented Feb. 11, 1969 in which X is of thegroup consisting of alkoxy radicals or halogen atoms, R is a monovalenthydrocarbon radical or halohydrocarbon radical, Z is a divalenthydrocarbon radical of from 2 to 8 inclusive carbon atoms and n has avalue of from 0 to 2, there being per molecule at least one halogen,alkoxy, or

radical.

In the formula above, where there is only one, two, or three Xsubstituents that are alkoxy radicals, halogen atoms, or both, theremaining R radicals can be any hydrocarbon or halohydrocar-bon radical.Also, where Z radicals are present, the remaining radicals attached tothe silicon atoms can be any hydrocarbon or halohydrocarbon radical, anyalkoxy radical, or any halogen atom.

Therefore, in the above defined formulae, the functional X substituentscan be methoxy, ethoxy, propoxy, isopropoxy, ibutoxy, isobutoxy, hexoxy,isooctaoxy, or octadecoxy, although for purposes of this invention,alkoxy radicals of from 1 to 4 carbon atoms are to be preferred. Thefunctional X substituents can also be any halogen atom such as chlorine,bromine, iodine, or fluorine. Accordingly, the non-functional Rsubstituents, if any, can be any rnOnOValent hydrocarbon andhalohydrocarbon radical such as methyl, ethyl, propyl, isopropyl, butyl,t-butyl, dodecyl, octadecyl, myricyl, pentyl, isopentyl, hexyl,isoheXyl, cyclohexyl, cyclopentyl, methylcyclohexyl, hexylcyclohexyl,cyclobutyl, cyclohexenyl, vinyl, allyl, methallyl, hexenyl, octadecenyl,S-phenylpropyl, B-phenylethyl, benzyl, chlorobenzyl,iodofi-phenylpropyl, chloromethyl, chlorobutyl, bromopropyl,3,3,3-trifluoropropyl, gamma-chloropropyl, (perfluoroethyl)ethyl,(perfiuoropentyl)ethyl, (perfluorononyl) ethyl, iodophenyl,u,a,a-trifluorotolyl, perfiuorocyclohexenyl, phenyl, tolyl, xylyl,ethylphenyl, mesityl, methylethylphenyl, n-propylphenyl, propylphenyl,isopropylphenyl, diethylphenyl, pentamethylphenyl, amylphenyl,butylmethylphenyl, propyldimethylphenyl, ethyltrimethylphenyl,diethylmethylphenyl, hexylphenyl, cyclohexylmethylphenyl,amylmethylphenyl, butylet'hylphenyl, butyldimethylphenyl,propylethylmet-hylphenyl, diphenyl, dipropylphenyl, naphthyl,l-methylnaphthyl, 2-methylnaphthyl, l-ethylnaphthyl, 2-ethylnaphthyl,phenylnaphthyl, anthracyl, 9-Inethylanthracyl, 2,3-dirnethylanthracyl,2,4-dimethylant-hracyl, 9-ethylanthracyl, bromophenyl, o-bromotolyl,m-bromotolyl, p-bromotolyl, o-chlorotolyl, m-chlorotolyl, p-chlorotolyl,2-chloro-mfluorotolyl, 2,6-dichlorotolyl, 4-bromo-o-Xyly1,dichloroxylyl, S-bromo-m-xylyl, Z-bromo-p-xylyl, Z-bromomesityl,3-bromo-o-tolyl, 2-bromo-1-ethylphenyl, 4-bromo-1,3- diethylphenyl,6-bromo-3-ethyltolyl, 2-bromo-4-ethyltolyl, 4-bromo-1-propylphenyl,4-bromo-l-isopropylphenyl, 4- bromo-1-methyl-3-isopropylphenyl, 4bromo-l tertiarybutylphenyl, 4 'bromo 1 tertiary amylphenyl,chlorophenyl, alpha-bromophenyl, betabromophenyl, 2-chloronaphthyl,1-bromo-3-chloronaphthy1, 2-chloro-1-methylnaphthyl, 1-bromo-8-methylnaphthyl, l-brorno-2,3-dimethylnaphthyl,1-bromo-4-methylnaphthyl, 1,10-di bromo-anthracyl,9,10-dichloroanthracyl, phenanth'ryl, 3- methylphenanthryl, and1,4-dimethylphenanthryl, among others.

In the above formulae, Z can be any divalent hydrocarbon of from 2 to 8carbon atoms. It is to be noted therefore that Z can be In the abovereaction, an intermediate compound of the formula [XmIRa-mSiCHzCHzSiO]t, is formed. This intermediate product is then appropriately heated inthe presence of a base and a rearrangement occurs, whereby the resultingcyclic has the formula xnnz-nsiomonzsm'x where X, R, and n are asdefined above.

Other cyclic silethylenesiloxanes of this invention can be prepared byreacting, (1) a vinyl silane of the general formula CH =CHSiX R' whereinX, m, and R are as defined above, with (2) a hydrogen disiloxane of theformula wherein R is as defined above, in the presence of catalyticplatinum.

In the above neaction, an intermediate compound of the formula [X R'SiCH CH SiR' O is formed. This intermediate product is thenappropriately heated in the presence of a base. The resulting cyclic hasthe formula CHE-CH2 xnR'z-nsi SiRz For purposes of this invention, it isto be noted that upon formulation of the desired cyclic, a linearbyproduct of the formula R! XS iCHzCHz-SiXmR m is evolved. Subsequentpartial hydrolysis in the presence of heat and a catalytic base willconvert said by-product to the desired cyclic, resulting in additionalyields of the cyclic organosiloxanes of this invention.

By the term partial hydrolysis in the above is meant a hydrolysiswhereby only 1 mole of water is employed so that it will react with twoX radicals of the above by-product.

Cyclic silethylenesiloxanes of this invention can also be prepared byreacting,

(1) the intermediate compound defined above of the formula [X R' SiCHCH- SiR' O with (2) 2 moles of a diol of the general formula Z(OH)wherein Z is as defined above, in the presence of a base and 1 mole ofwater.

In the above reaction, thermal cracking in the presence of a baseresults so that the composition yielded is a strained ringdepolymerization product of the formula wherein Z and R are as definedabove.

In the process for obtaining the intermediate compound used in thisinvention, the catalytic platinum is ordinarily used in concentrationsof from 1X10" to 1 10*' mole per mole of vinylsilane. The commercialform of the catalyst is the hexahydrate, H PtCl -6H O, and this form iscompletely satisfactory. Since relatively minute amounts are used, it isbest to employ a solution of the catalyst, e.g. in isopropanol or thedimethylether of diethylene glycol.

It is also to be noted that any desired X and R radicals in thecompositions of this invention are readily and easily obtained byselecting the appropriate vinylsilane reactant. Illustrative of suchreactants are the compounds Also illustrative of said reactants are thecompounds,

(Cl SiCH=CH CH CH O ClSiCH=CH (F) SiCH=CH- (Br) SiCH=CH CH CH CH O ClSiCH=CH (CH CH O) (C H )FSiCH=CH (CH O) (CH ClSiCH=CH among others Whenthe necessary siloxane intermediate is formed, if appropriate, it ispartially hydrolyzed and then cracked. After partial hydrolysis andprior to alkaline cracking" the partial hydrolyzate is neutralized orwashed free of substantially all of any acid catalyst or by-productresidual acid which may be present prior to the said cracking"operation.

It is preferred that the partial hydrolyzate then be stripped of anylow-boiling solvent which may be present and the cracking" catalyststhen added. It is to be noted that no catalyst is required in thecracking" operation, however inclusion of a catalyst will preferablyincrease the yield of strained ring cyclics. Illustrative of thecracking catalysts that can be used on the non-acidic siloxanesubstrates are CH CH CH CH Li, sodium methoxide, Na SiO Na SiF CaO, CaCOCa(OH) BaO, and Na CO among others. Although any of the above catalystscan effectively function in this invention, the preferred catalysts arethe alkaline earth metal oxides rather than the alkali metals, andparticularly BaO, due to the increased yield of products and strainedrings obtained. The selection of a catalyst can also have a significanteffect on the concentration of strained ring cyclics produced. Dependingupon the choice of catalyst, e.g., whether it is a weak or strong base,varying yields of strained rings are obtained. For example, when orequivalent moderately strong or very strong bases are used, the yield ofstrained rings will be significantly lower than when a weak base such asBaO is used, due to Si-C redistribution in addation to the desiredSi-O--Si redistribution.

The temperature required for the cracking operation is in the range offrom 200 to 420 C. Atmospheric pressure can be used when the product isone of the lowboiling cyclics, e.g., when all or most of the X and Zradicals are of low molecular weight. When the product is of relativelyhigh molecular weight it is preferred to operate under reducedpressures.

The cyclics defined above are both derivatives of the reactive1,2,5-oxadisilacyclopentane heterocyclic system disclosed in US. Patent3,041,363, June 26, 1962, however those disclosures were limited toderivatives in which the two silicon atoms were fully substituted withalkyl and aryl substituents. The compounds of this invention are uniqueand distinctive in that they contain silicon atoms substituted withfunctional radicals.

This invention also relates to novel cyclic silethylenesiloxanesprepared by reacting.

(1) a vinyl silane of the general formula CH CHSiX wherein X is asdefined above, with (2) a hydrogen siloxane of the general formula XSiH, wherein X is as defined above, in the presence of catalyticplatinum.

In the above reaction, an intermediate compound of the general formula XSiCH CI-I SiX is formed. This intermediate compound is then reacted with2 moles of a diol of the general formula Z( OH) wherein Z is as definedabove, in the presence of a base and 1 mole water. Partial hydrolysisand thermal cracking is as previously defined. Rearrangement occurswhereby a compound of the formula \O\ /CH: 052 ./O\

results.

It is to be noted that the above intermediate compound can also besimilarly reacted with appropriate monofunctional alcohols to obtaincyclics of the formula The following examples are intended to aid thoseskilled in the art in understanding and practicing this invention. Theexamples do not delineate the scope of the invention.

Example 1 43.0 g. of

(CH3): [(CHaOMSiCHKJHziIzO was reacted with 29.2 g. of

(CHah-C-OH CH2 (3H2 (CHa)z( ]OH in presence of 1.8 g. of water in a 250ml. distillation flask and a catalytic amount of NaOCH was added. Theflask was attached to a distillation column and heated to a temperatureof 260 to 300 C., removing CH OH as it 6 formed. After 10 to 12 hours,17.3 g. of CH OH was removed. Subsequent alkaline cr-acking at atemperature of 300 to 340 C. yielded a compound of the formula (CHM CH;2-0112 0- -CH2 on. o/ oo-cm (CH2): being collected at C., and 0.3 mm. Hgpressure.

Example 2 18.6 g. of hexamethoxydisilethylene, 29.2 g. of2,5-dimethylhexane-2,5 diol, and a trace of NaOCH was added to a 250 ml.distillation flask. The flask was attached to a distillation column andheated to cause alcoholysis. The mixture was further heated to 260 C.for 1 hour and M5 g. of CHgOH was collected. 1.8 g. of water was thenadded. Subsequent alkaline cracking at a temperature o 300 to 360 C.yielded a compound of the formula being collected at C., and 0.05 Hgpressure. The compound had a melting point of 7880 C.

CHaCHaCHzCHeO CHzCHz l omomomomo oomorncmorh was collected at 119 C.,and 0.01 mm. Hg pressure.

/0 CHzCHzC HaCH;

Example 4 To a 250 ml. distallation flask was added 98.5 g. of [(CH O)SiCH CH Si(CH 10 and 0.05 g. of Na0CH The flask was then attached to adistillation column and heated to a cracking temperature of 250 to 285C. The volatile materials were collected and upon redistillation acompound of the formula CHaO CHzCHa CH2 orno o oH, was collected at 50to 60 C. at 0.6 mm. Hg pressure.

Example 5 236.0 g. of OHFCHSi(OH OCH and 6 drops of H PtCl was added toa 500 ml. flask. The flask was heated to 81 C. and 120.8 :g. of

(3111] HSiO 4 was slowly added. The reaction was exothermic and thetemperature rose to C. The solution was stirred until cool and infraredanalysis indicated a compound of the formula 100 ml. of

CH3] [CH3O(CH3)zSiCH2CH2SiO 4 and 1.9 g. of BaO was added to a 200 ml.flask. The flask was heated in a range of from 390 to 420 C. A yield of81.0 g. of a compound of the formula CH: CH2CH2 CH3 was obtained.

Example 6 490 g. of CH =CHSi(CH Cl and 6 drops of H PtCl was added to a1 liter flask. The mixture was stirred and heated to reflux and 238.2 g.of

was slowly added. This was then heated to 240 C. and cooled to roomtemperature and a compound of the formula a)a" (IJHzOHZSiCI -Si-O JHa |4was obtained. 100 ml. of

r H3): CHzCHzi-Cl S iO substituted for the silane in Example 6,compounds of the formulae When Br, I and F are substituted for thecorresponding halogen in Examples 6 and 7 equivalent results areobtained.

Example 10 Addition of vinyl trimethoxy silane to [CHaSiOh in thepresence of a platinum catalyst will give a struc- 1 J 4 ture of theformula and 0.5 cc. of butyl borate was added to a 1 liter flask.CHaSi-O- This was heated at 365 to 390 C. for 8 /2 hours andCLHNHZSKOCHQLL 93.4 g. of a compound of the formula CH: CHPCHZ C1 100ml. of this intermediate was cracked in the presence of numerouscracking catalysts at temperatures in a range of from 300 to 420 C., toobtain the desired novel CH3 0 CH; cyclic of the formula was collected.Analysis showed 75 percent of the product 4? E E to be strained ring. SiSi In the above, when no catalyst was used and the mix- \OCH ture washeated at 360 to 440 C., 97.5 g. of the novel cyclic was obtained withpercent of the products Varying conditions and results are tabulated inthe folstrained rings. lowing table.

Yield of Percent Cracking Temp. Catalyst Products, Products time, range,

g. Strained hours O.

ring Number:

1 0.1028 g. Na,s1o, 47.2 2-4 2 0.1055 g. Na4SlO4- 42.1 11 3 52.3 19 4-45.8 12.5 5- 65.0 35 s 62.8 45 7- 33.2 1 s. 41.1 1 94-- 60.4 41 10--65.3 42 11 79.9 45 12.- 72.1 22

Example 7 That which is claimed is:

When 1 mole of the cyclic compound of the formula 1. A cyclicorganosilicon compound of a formula selected from the group consistingof and 0 F l Z SlCHzCHzSl Z L l in which X is a monovalent radicalselected from the group consisting of halogen atoms and alkoxy radicals,

R is a monovalent radical selected from the group consisting ofhydrocarbon radicals and halohydrocarbon radicals of from 1 to 12inclusive carbon atoms,

Z is a divalent hydrocarbon radical of from 2 to 8 inclusive carbonatoms, and

n is an integer of from 0 to 2 inclusive, there being per molecule atleast one silicon bonded halogen, alkoxy, or

{-0 Z L0 radical. 2, The cyclic organosilicon compound as recited inclaim 1 wherein the formula is XnR'Z-nSlCH2CH2SiXnR2-n 3. The cyclicorganosilicon compound as recited claim 2 wherein the formula isCHaCHzCHzCHzO CHaCHz 4. The cyclic organosilicon compound as recitedclaim 2 wherein the formula is C Ha 5. The cyclic organosilicon compoundas recited in claim 2 wherein the formula is CH; CHaCHa S1 CH:

CHzCHz OCH:

6. The cyclic organosilicon compound as recited in claim 2 wherein theformula is CH; CH2CH2 CH 7. The cyclic organosilicon compound as recitedin claim 1 wherein the formula is 8. The cyclic organosilicon compoundas recited claim 1 wherein the formula is CHz-C-O O-G-CHz SiCH2CHzSiCH2CO O O-C-CHz 9. A method for making cyclic organosiloxanes of theformula and 0 0 i SiCHzOHQSi 12 -o 0 0 (A) comprising heating a compoundof the formula X is of the group consisting of alkoxy radicals or ahalogen atom, and each R is a monovalent hydrocarbon or halohydrocarbonradical of from 1 to 12 inclusive carbon atoms,

Z is any divalent hydrocarbon of from 2 to 8 inclusive carbon atoms,

m is an integer from 1 to 3 inclusive,

n is an integer from 0 to 2 inclusive, and

x is an integer of at least 3,

(B) in the presence of a base selected from the group consisting oforganolithiums of the formula RLi, in which R" is an alkyl or arylradical of from 1 to 12 inclusive carbon atoms, sodium alkoxides of theformula NaOR", in which R" is an alkyl or aryl radical of from 1 to 12inclusive carbon atoms, Na SiO Na SiF CaO,

' CaCO Ca(OH) BaO, and Na CO and thereafter recovering said cyclicorganosiloxane compound.

10. The method as recited in claim 9 wherein Compound 2 in which m is 3is heated in the presence of 2 moles of a diol of the formula Z(OH)wherein Z is any divalent hydrocarbon of from 2 to 8 carbon atomswhereby a compound of the formula SiCHzCHzSi Z is formed.

11. The method as recited in claim 9 wherein Compound 3 in which m is 3is heated in the presence of 2 moles of a diol of the formula Z(OH)wherein, Z is any divalent hydrocarbon radical of from 2 to 8 carbonatoms whereby a compound of the formula I -O O O is formed.

12. The method as recited in claim 9 wherein the base is BaO.

References Cited UNITED STATES PATENTS 2,777,869 1/1957 Bailey et a1260-4482 3,041,362 6/1962 Merker 260-4482 3,053,872 9/1962 Omietanski260-4482 3,294,740 12/ 1966 McVannel 260-465 XR 3,355,475 11/1967 Baney260448.2

TOBIAS E. LEVOW, Primary Examiner.

I. P. PODGORSKI, Assistant Examiner.

US. Cl. X.R. 260-465, 448.8

